Solution of titanic hydroxide in hydrogen peroxide



Patented Feb. 14, 1939 UNITED STATES SOLUTION OF TITANIC HYDROXI'DE 1N HYDROGEN PEROXIDE Samuel Katzoif, Hampton, Va.. and Reuben Roseman, Baltimore, Md.

No Drawing.

Application June 8, 1937,

Serial No. 147,146

14 Claims.

This invention relates to a new composition of matter, viz. a solution of titanic hydroxide in hydrogen peroxide which may be appropriately designated as a pertitanic acid sol, together with 5 related solutions, jellies and gels, and to processes for obtaining the same.

One object of the invention is to provide a solution of titanic hydroxide in hydrogen peroxide which solution is adapted to a variety of 10 applications in the are and industries. For example, it is useful in mordanting and tanning; for weighting and delustering silk, rayon and other fibrous materials; for impregnating wood, textiles, paper, etc.; for bleaching purposes; and

15 for medicinal purposes. It supplies a translucent adherent coating, where that is desirable, for the surfaces of materials such as wood, glass, ceramics, etc.

Another object of the invention is to provide a 20 method for dissolving titanic hydroxide in hydrogen peroxide, which method may be practiced not only with the ingredients in bulk, but also on a microscopic scale as well; as for instance in the fibers of a textile or leather material. The invention thus gives rise to new methods of mordanting or tanning.

Other objects of the invention are to provide a solution, and to eifect the solution, of a mixture of titanic hydroxide and ferric hydroxide in hy- 30 drogen peroxide.

ed to a variety of applications in the arts and industries similar to those indicated above.

Other objects of the invention are to produce related jellies, useful for such purposes as the above, either directly, or after dilution with water to form solutions similar to the above, and gels, useful in catalysts.

Still other objects and uses will be obvious to I those skilled in the art from the following de- 40 tailed description of the invention.

We have found that freshly precipitated and well-washed titanic hydroxide dissolves in dilute hydrogen peroxide, to give a clear yellow solution.

The titanic hydroxide may be obtained by any of several known methods. One, for example, is to add a 0.25% ammonia (NHa) solution to a 0.6% solution of the double oxalate of potassium andv titanium [KzTiO(C2O4) 2.2H2O] in the cold 50 to produce orthotitanic acid [Ti(I-I)4]. Ac-

cording to our method, the titanic hydroxide is first thoroughly washed with a good grade of wash water, preferably distilled. Any of the usual methods of washing such precipitates is 5 satisfactory; it is desirable, however, to avoid This solution is likewise adaptlong exposure to high temperatures, or extensive drying of the precipitate at any time. Ordinary washing by decantation is, for example, satisfactory, provided that electrolytes are substantially removed. 5 Hydrogen peroxide is next added to the washed titanic hydroxide. It will readily dissolve, or peptize, the latter, giving a clear yellow solution. The time required depends on the proportions of the ingredients used, and on the temperature. For example, 50 cc. of a suspension containing 0.0035 mole of Ti(OH)4 treated with 0.4 cc. of 30% H202 (0.0039 mole) becomes clear within an hour at room temperature, or within a few minutes when warmed. Larger proportions of hydrogen peroxide hasten solution and give clearer solutions, while lesser proportions give solutions with pronounced opalescence. If the titanic hydroxide precipitate is relatively concentrated, it will tend to give a yellow jelly or gel instead of a yellow solution.

Small amounts or traces of base aid solution, especially where the titanic hydroxide is impure. Indeed, we have discovered that, with varying proportions of base and of hydrogen peroxide, 25 colloidal solutions can be made ranging between the colloidal solutions above described and the known molecular (non-colloidal) solutions of pertitanates. From the foregoing, it will be obvious that the amount of base used to obtain the above mentioned colloidal solutions will be less than sufiicient to produce molecular solutions; in other words, the amount of base useful in the present invention is less than the stoichiometric proportion operable to make such molecular solutions with the titanium hydroxide.

The solutions have colloidal properties, as exemplified by failure to diffuse through a collodion membrane, and colloidal precipitation or gelling by electrolytes. 4Q

Ferric hydroxide alone will not dissolve in hydrogen peroxide. According to our invention, however, co-precipitated and well-washed titanic hydroxide-ferric hydroxide mixture will dissolve in hydrogen peroxide, to give a clear brown solu- 4,5 tion. For example, cc. of a suspension containing 0.0028 mole of Ti(OH)4 and 0.0007 mole of Fe(OH)a, treated with 1 cc. of 30% H202 (0.010 mole), becomes clear within an hour at room temperature, or within a few minutes when 50 warmed. As before, small amounts or traces of base aid solution, especially where the titanic hydroxide-ferric hydroxide mixture is impure. The properties of these solutions are, in general, the

same as those made from titanic hydroxide alone. 68

. In ,fact, there-is a. close correspondence between,

the properties 01 the TKOH) 4-' -=-Fe (OH)a' mixture.

and the. TKOHM. I

such methods as adding I It is: to be understood that where ferric or ion solutions by boiling and/r. evaporating, or by electrolytes cautiously,

or, adding alcohol. I II I I I I I I I I I The solutions, jellies, and gels described can be producedin theinterstices or within the fibers of leather, textiles'or the like. .'Ihus,aprecipi-I1 I I I titanium hydroxides, I and mixing hydrogen pe'rtate oftitanic-hydroxideis first produced in the material, as, for-example, by soaking it in a dilute I solution of a 'titanlum 53113; and; then; adding. a

dilutesolution of base, using, for example, the

.same compounds previously specified (potassium oxalate and ammonia). The material; I I I is; Washe'cand then treatedwlth hydrogen perox,

. ide .iInIaccor'dance with our method, j I I I Theterm hy'dro'soPI used; herein maybe de fined as a colloidalsystem in whichthe dispel? titanium sion medium'ls principally water. i

droxide colloidally dispersed therein by; cO-m'e- I cular solution.

' I cipitation and co-solution. I

i 5. The process of; obtaining a I 4; A :colioidal; solution comprising hydrogen peroxide, a base, titanieh-ydroxideand ferric hy'-" droxide colloidally dispersedtherein by ,co-pre-- cipitation andco-solutionlnuw. I colloidal solution I of, titanium hydroxide, and iron hydroxide in hy-. drogen' peroxide, which comprises ce-precipitat ing the said hydroxides and mixing the co-precipitated hydroxides with hydrogen peroxide.

6. The process of obtaining h. hydrosol of titanium hydroxide and iron hydroxide in hydrogen peroxide, which comprises co-precipitating the said hydroxides and mixing the co-precipitated hydroxides with hydrogen peroxide in the presence of base.

. 8. The process of making a gel, which comprises: 'corprecipitatingiron and I titanium hydroxides, concentrating the: same-, I

. and then mixing hydrogen peroxide with the concentrated oopreci'pitate'd titanium hydroxide I ide and hydrogen peroxide. I I I I I I 7. The process or making a colloidal jelly gel which comprises oo-precipitating iron and 3 titanium hydro ddes, concentrating the same, 'andthen mixihghydrogen peroxide wlththe con-' centrated II co-precipitated and iron hydroxide. I

colloidal jelly or and'iron hydroxidein the presence of: base; i I I 9. The processor making a colloidal jelly or gel; which comprises co-precipitatingiron and I oxide with the co-precipitated titanium hydroxideand iron hydroxide in the presence electro lyte.

10. The process of obtaining a colloidal solotion; containing titanium hydroxide in dispersed I phase, which comprisespre'cipitatihgorthotitanic I y I acid 'troma solutionof a titanium compounds I washing the fresh precipitate to remove harmliul electrolytes; and then I mixing hydrogen per oxide with said precipitate whilemoist. I I

, titanium hydroxide 1 1. The process of obtaining a'colioidal. soluseparating the precipitate, and"; than adding hy moist; and in the presence of a base, said base'being less thanan' amount I 12; A colloldalgelcomprising titanium hydrox tion containing titanium hydroxide in: dispersed I l I I I I phase, which comprisespre cipitating orthotitanic i 3 acid from a solution of'a titanium compound,

. a Y drogenperoxide to ,the'saidprecipltate:whilei which would cause mole- I I 13. The process of treating aporousim'aterial 14. The process of treating a porous material which comprises preparing within its pores or interstices moist co-precipitated titanium hydroxide and iron hydroxide and subsequently adding hydrogen peroxide.

SAMUEL KATZOFF. REUBEN ROSEMAN.

whlch'cmnprisesprepiaring a :moist precipitated of titanium hydroxide-within :its pores or in II .terstlces: and subsequently adding "hydrogen I I 1 peroxide. 4o I I 

